Cupriferous azo-dyestuffs



United States Patent CUPRIFEROUS AZO-DYESTUFFS Henri Riat, Arlesheii'n, and Paul Dreyfuss and Fritz 2,763,640 Patented Sept. 18, 1956 senting a benzene or napthalene radical to which the azo linkage and the aminogroup are bound in para-position, are linked together at their amino groups to form the corresponding urea or triazine derivative, and if desired,

Oesterlein, Basel, Switzerland, assignors to Ciba Lim- 5 the dyestufi so obtainFd or the i dyestufi of the Red, Base], Switzerland, a Swiss firm Formula 5 .18 treated with an agent yielding copper.

The linking together of the two aminoazo-dyestufis to N Drawing p flm t Descembel 21, 1953 form the urea derivative may, for example, be carried out Sena! s4 in the usual manner with phosgene, advantageously by Claims priority,application Switzerland introducing phosgene into an aqueous alkaline solution December 24, 1952 which contains the two dyestufis. In this manner there 302mmz60 148) are generallyobtained, in addition to the asymmetrical urea derivatives which are formed predominantly, a small This invention providesnew directdyeing azo-dyestuffs amount 0f symmetrical urea derivatives Which o n t and cupr-iferous azo-dyestuffs,'for example, the dyestuifof 11511311) have y disadvantageous efiect- A Practically the constitution unitary asymmetrical urea derivative is obtained when, (1) COOCu- E kaN NL NGM H000 H033 SOaH The new dyestuifs contain more than one azo linkage instead of reacting the two aminoazo-dyestuffs with phosand an ortho-hydroxy-ortho-carboxyazo-grouping, which gene, one of the dyestuifs is converted, advantageously is capable of forming metal complexes or is metallized. the dyesttifi of the Formula 4, for example, by means of The dyestufis which contain a, grouping capable of forming chloroformic acid phenyl ester, into the phenylmrethane, metal complexes correspond to the general formula and the latter is condensed with the other aminoazo-dyestufi. (2) OOOH H0 The linking together of the two-aminoaz'o-dyestuffs t0 form the triazine derivative is advantageously carried out in stages by means of a c'yanuric halide, more especially H038 cyanuric chloride. The condensations with the cyanuric halide may be carried out in any desired order of succesin which R1, and Y ivrepresent benzene di l h sion, for example first with the dyestuff of the Formula radical R1 containng in para-position with respect to the 5 f f Wllh theidyestllfi 0f the Formula In m azo linkage a hydroxyl group and in ortho position to Case? 1t 3 f advaIftage t0 addpto aqueous Teactlon the latter group a carboxylic acid group, the radical Rs m b i l amounl of an Inert, Water-891111316 being bound in the 1:2:4-p0sitionsrespectivelyto the azo Orgafilc Solvent 9 f CXHIIIPIB, as aceiofle- Thls P linkage, the carboxylic acid group and X, R2 representing a 40 f33d11re 1efld5 9 especlflny Valuable results, for pl benzene or napthalene radical to which the azo linkage m f; P F Q Y fiS f the ula 3 With and the bridge member X are bound inpara-posi tiomand of F p T ammo aZO dyestufi 0f the Formula X represents an H CQ NH. b id or a i i 5. The third halogen atom remaining attached to the radical bound by their to R2 and R triazine ring may, if des red, be exchanged for a hydroxyl The cupriferous dyestuffs correspond to the formula p, 1' he eac lons may be carried out at; that atom, for example, it may be reacted with ammonia or (3) Coofiau? an aromatic amine such as aminobenzene.

Aminoazo-dyestuffs of the Formula 5 are obtained by R N:N R2' X*'R3 -N=N NH-Y coupling a diazotized aminobenzene, which contains in Hogs; ortho-p'os'ition to the amino group a carboxylic acid group and in para position to the amino group a substituent coni s van vertible into an -NH2 group, with a 2-phenylamino -8- bound in complex union the aforesa d siibstituent ll'llO an- NHzgroup. As diazo- The invention also includes Process for making the component there comes into coiisiderationmore especial new yes this nitro compound there may be used the corresponding fonnulae acetylamino-compound, and in this case after the coupling,

(4) hydrolysis of the acetylamino group must be carried out and instead of reduction of the nitro group.

The 2-phei1ylamino-8-hydroxynaphthalene 6 sulfoni'c (5) 00011 HO acids required for making the aminomonoazo-dyestuifs of the Formula 5 may contain further sub stituents in the HN-RPNi-NT' NH-Y phenyl radical, for example, halogen atoms such as chlorine, or methyl or methoxy groups. In the case of the cupriferous dyestuffs made by the present process the t b nzene radicals the presence of a group imparting solubility in the phenyl izd iz l l h i dn t a in igg iii i -2 55mm? with respect to the rafiical of the phnylafnlno group f f i a sulfonlF azo linkage a hydroxyl groupand in OIthO-POSllIlOI-MIO" the acld P BaFbOXKYhC acld 0T sulfonlc 301d amlde R 15 latter group a carboxylic acid group and the radical R3 p i y advantageous, and as @Xamples of such lcoupllnig being bound in the lz 2z4-position respectively to the azo linkage, carboxylic acid group and amino group R2 reprecorhponents there may be mentioned 2-phenylamino-8- hydroxynaph-thalene-6:3- or 6:4-disulfonlic acid and also Z-phenyl-amino-8-hydroxynaphthalene-6-sulfonic acid 3'- or -4-ca.rboxylic acid.

The dyestuffs of the Formula 4 may contain in the radical R1, advantageously in ortho-position with respect to the hydroxyl group, a further substituent, for example, a halogen atom, a methyl group or a sulfonic acid group. The radical Rz may also contain further substituents such, for example, as a methyl or methoxy group, a halogen atom such as chlorine, or a sulfonic acid amide group. As examples of suitable aminoazo-dyestuifs of the Formula 4 there may be mentioned in this connection: 4-amino-4'- hydroxy 1:1 azobenzene-B carboxylic acid, 2-chloro-4- amino-4-hyclroxy-l:lazobenzene-3'- carboxylic acid, 2- methyl-4-amino5-metl1oxy-4-hydroxy-l:1' azobenzene- 3'carboxylic acid, 4-amino-4-hydroxy l:l'-azobenzene- 3-carboxylic acid-5-sullionic acid, 2-methyl-4-amino-5- methoxy-4'- hydroxy l:l'-azobenzene-3'-c-anboxylic acid- 5'-sulfonic acid, and 4-amino-4'-hydroxybenzene-1'-azol-naphthalene-3-carboxylic acid-6- or -7-sul'fonic acid.

The dyestuffs of the Formula 2 are suitable for dyeing and printing a very wide variety of materials, especially cellulose-containing fibers. They can be treated with agents yielding metal, and the treatment may be carried out by the usual known methods. In the case of dyestuffs possessing sufficient solubility, and especially when the dyestuffs contain insufficient groups imparting solubility to be well suited for dyeing by the usual direct dyeing methods in the form of their complex me'tal compounds, the treatment with the agent yielding metal is advantageously carried out on the fiber or in a single bath in part in the dyebath and in part on the fiber. A further advantageous dyeing method in the case of those dyestuffs of the Formula 2 which yield sparingly soluble metal complexes, consists of using a dyebath prepared with the dyestuif, an hydroxy-alkylamine, a metallizing agent stable towards alkali, and advantageously a compound which contains the anion of a phosphoric acid. Methods of this kind are described in U. S. Patent applications Serial Nos. 319,773 and 319,774.

However, especially valuable results are obtained with the dyestuffs formed by treating a dyestulf of the Formula 2 with an agent yielding copper, or with the cupriferous azo dyestuffs of the Formula 3 obtainable from the coppered intermediate dyestuffs.

The treatment of the dyestuffs of the Formula 2 or the intermediate dyestuff of the Formula 5 with an agent yielding metal can be carried out by the customary methods. ample, with a salt of divalent copper in a weakly acid aqueous medium. The dyestuffs can also be metallized by methods in themselves known in which the metallization is carried out in an aqueous medium at a raised temperature with the use of copper tetramrnine complexes in the present or absence of an excess of amine or ammonia.

As the dyestuffs of the Formula 2 contain in the radical R1N=N--R2 an orth'o hydroxy carboxylic acid group, this group may also be coppered. It may be de- The metallization can be carried out, for exsirable so to carry out the treatment with the agent yielding metal that the formation of a complex takes place also in the aforesaid group of the dyestuff. In general, how ever, it is advantageous when no metallization occurs at the 'ortho-hydroxy-canboxylic acid grouping.

With regard to the formulae of the cupriferous dyestuffs given herein, these formulae undoubtedly represent the correct s'toichiome'tric proportions of copper and the correct position of the copper atom in the complex, but

the distribution of the main and secondary valencies in p O OH 1 the complex union of the metal has not yet been established with certainty.

The new cupriferous azo-dyestuffs corresponding to the general Formula 3 can be used for dyeing and printing a very wide variety of materials such as wool, silk, leather and especially cellulose-containing fibers such as cotton, linen and also artificial silk and staple fibers of regenerated cellulose, and if desired, in the case of those dyestuffs which contain an uncoppered orthohydroxycarboxylic acid group, they may be treated with an agent yielding metal on the fiber or in the dyebath.

In the case of those cupriferous dyestuffs of the Formula 3 which are too sparingly soluble for application by the usual direct dyeing processes, they are suitable for use in such processes when applied from neutral to alkaline dyebaths, which have been prepared from sparingly soluble complex copper compounds of direct dyeing dyestuffs, certain aliphatic amines which contain at least one amino group separated from a hydroxyl group by two carbon atoms (for example, 1:2-di-(fi-hydroxyethylamino)-ethane), and phosphorus compounds derived from acids of phosphorus having the constitution in which m represents a whole number (see also the specification hereinbefore mentioned).

By means of the cupriferous dyestuffs of the Formula 3 and the dyestuffs of the Formula 2 when they are metallized on the fiber, there are obtained dyeings which are distinguished by their especially interesting tints and in general by their unexpectedly good properties of fastness, above all by their good fastness to light.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

' Example 1 55.8 parts of the monoazo-dyestuff, obtained by coupling diazotized 5-acetylamino-2-aminobenzene-1carboxylic acid with Z-phenylamino-8-hydroxynaphthalene- 6:3'-'disulfonie acid in an alkaline medium, followed by splitting off of the acetyl group by heating the product in sodium hydroxide solution of 4 per cent. strength, are dissolved together with 25.7 parts of 4-amino4-hydroxyl:l-azobenzene-3'-carboxylic acid with the addition of sodium carbonate in 2000 parts of water. Phosgene is introduced into the resulting solution at 3540 C. until the free amino-compound can no longer be detected. By the addition of sodium carbonate the reaction mixture is continuously maintained weakly alkaline. As soon as the reaction is finished 10 parts of sodium chloride are added for every 100 parts by volume of reaction mixture, and then the dyestuff is filtered off.

The dyestuif paste so obtained is stirred with 2000 parts of water and sulfuric acid is added until the reaction is weakly acid to Congo. After the addition of 25 parts of crystalline copper sulfate the whole is treated for about one hour at 90 C. The dyestulf is then filtered off, washed with sodium chloride solution of 10 per cent. strength, converted into its sodium salt advantageously by means of sodium carbonate, and dried. It is a blackbrown powder which dyes cotton brown tints which are fast to light.

By using, instead of 4-amino-4'-hydroxy-l:l azobenzene-3'-carboxylic acid, 2-chloro-4-amino-4'-hydroxy- 1:l-azobenzene-3'-carboxy1ic acid a similar dyestuff is obtained, which corresponds to the formula Example 2 Thedycstufi so obtained may, advantageously Without To a fine suspension of 19 parts of cyanuric chloride inmrmediate t confined i .itscomplex in 400 parts of ice water is added a neutral solution of the per a weakly acid solutlonim the usual} p" sodium salt of 55-.8 parts of the .monoazo-dyestuif oband thecopper'compound may beconvefted'lmo Its tained by .coupling diazotized -4-nitro-1-arninobenzene-2- 5 scdmm i "cqppertfre {he cupilfemusdyfi carboxylic acid with 2-phenylann'no-8-hydroxy-naphtha- Stuff are d1stmgm.shd esPeclanylmiltari'y i lene-6:3'-disulfonic acid and then reducingthe nitro group dyestuffs areddentlcal mam f i of to an amino group The Whole is Stirred at about 50 the-corresponding dyestuifsobtamable as described 1n EX- and the reaction mixture is neutralized by the dropwise ample E l 4 .addition of 50 parts of sodium carbonate solution of 10 10 xamp e per cent. strength. After one hour, there is added to the The procedure is similar to that described in Example primary condensation product a neutral solution of the 2 except thatthe sequence of operations is changed by sodium salt of 26 parts of 4-amino-4'-hydroxy-lzl' azofirst *condensing the cyanuric chloride with the amino- 'benzene-3'-carboxylic acid, and the'whole is stirred .for hydroxy-azobenzene carboxylic acid and then with the 4hours at 30 C. with the gradual addition of azo-dyestufl? from 2-phenylamino-8-hydroxynaphthaleneparts ofsodium carbonate solution of 10 per cent. strength. 6:3-disulfonic acid, theremaindertof the procedure being There are then added 120 parts .of aniline and 15 parts of the same. The same dyestuff is obtained. crystalline sodium acetate, and the Whole is heated for .Dyestutfs having similar propertiesare obtained by retwo hours at 80 C. The reaction mixture is rendered 20 placing in the second .amino-azo-dyestufi? the Z-phenylalkaline with sodium carbonate, and the dyestutf is preamino-.8=hydroxynaphthalene-6:3'-disulf0:nic acid by 2- cipitated With sodium chloride and filtered oif. 'phenylamino- 8 hydroxynaphthalene-6-su1fonic acid-3- For the purpose of converting it into the copper .comcarboxylic acid or by 2-phenylamino-.B-hydroxy-naphplex the dystuff is dissolved in 2000 partsof .warm Water, thalene-6-sulfonic acid-4'-carboxylic acid. and the solution is mixed with dilute sulphuric acid until 25 By using 2-chloro-4-amino-4'-hydroxy-l:1-azobenzenethe reaction becomes --Weakly acid to Congo. There are 3'-carboxylic. acid ,as starting material, "a similar dyestutf then added 25 parts of crystalline copper sulfate and the is likewise obtained. It corresponds to the formula O0O-Cu-0 S0311 whole .is heated for .one hour at80 C. The resulting copper complex is then filtered off. and converted intoits Example 5 .sodium salt by a .methoddnitselfknown. .Afteriwork- 28 parts of 4-arnino-4'-hydroxy-1:lflazobenzeneaying up and drying the product, there is obtained a browncarboxylic acid in the form of the sodium salt are disblack powder, which dissolves in water With a red-orange solved in a mixture of 150 parts of acetone and parts coloration and dyes cotton'brown tints which are fast .to of \water. The solution isaddedat 0 C. to'a solution of light. The dyestuff corresponds to the formula 20 'parts of cyanuric chloride in 140 parts of acetone.

Example 3 After 20 minutes, .the product is filtered oil andwashed I i 'th benzene and water. In this manner there is obtained 29.2 parts of 2+chloro-4-am1no-4-hydroxy=1 :"1 azoben- W1 zene-3'-carboxylic acid are dissolved *in 1000 parts of the compound of the formula water with the addition of the quantity -'of-sodium-car- CI bonate necessary for neutralization. The solution is stirred with 15.6.parts of .chloroformic acid phenyl ester until the odor of the ester disappears. Further sodium HOQTN=NONHTO\ carbonate isadded until the SOIUtiOI'lQlSOIllY weakly-acid N0 (pH=6) and further chloroformic acid phenyl ester is H00 1 5 introduced dropwisevuntil the product is no longer capa 1 ble of being diazotized. The urethane formed is filtered in an excellent state of purity. 41 parts of the latter off with suction and introduced into a neutral solution of product are stirred with .55 parts of the dyestuif of the f55;8:parts of .thedyestutf obtainedbyl coupling diazotized formula =4-acetylamino-1-aminobenzene-2-carboxylic .acid with 2- '.phenylamino 8'hydroxynaphthalene-6:3'-disulfonic acid illolomoumo 30:11 andzthen splitting oil the acetyl group. After the =addi- 1 tion of 16.8 parts of sodium bicarbonate, the suspension C is stirred at 50-60" C. until a rtest portion is no longer diazotizable and even after being heated with :;sodium carbonate solution for a short time is no longer diazotiza- 1 The dyeslllfi is k dup in the usual manner. It in aqueous acetone of 50 per cent. strength. The suspeny cellulose-containing fibeTS by the g bath Or sion is neuralizediwith triethylamine and stirred at 40 C., Z-bath after ecoppering process level brown :tints. The while maintaining the mixture neutral by the addition of dyeings-are distinguished by their good-properties of fastfurther quantities -.of triethylamine, until no violet byness. products can he=detected in a paper chromatogram of a test portion. The dyestutf formed is then precipitated by Example 8 the addition of further acetone, whereby any yellow byproducts are retained in solution. The mixture is filtered, 1 Parts of the aminoazo dyesiufi of the formula and the filter residue is washed with acetone. The residue is a loose dark brown powder, solutions of which dye H0 -N=N -NHz cotton brown tints which are fast to light.

The dyestutf is identical with a dyestuif which is ob- H000 tained as described in Example 2 with the omission of 1 the heating of the intermediate product described in that SO H example with aniline and sodium carbonate.

are dissolved in 800 parts of water with the addition of the quantity of sodium carbonate necessary for neutralization and condensed with 19 parts of cyanuric chloride with ice-cooling, whereupon the reaction product is neu- A similar dyestutf is obtained by starting from 2-chloro- 4-amino-4'-hydroxy-l l-azobenzene-3'-carboxylic acid, instead of 4-arnino-4'-hydroxy-1: l'-azobenzene-3-carboxyhc and. Example 6 tralized with about 50 parts of a sodium carbonate solution of 10 per cent. strength. To the resulting sodium Parts Cyanunc ch1nde are condensed q salt of the primary condensation product there 'is added Ous Solutlon known manner Wlth 26 Parts of a neutral solution of 55.8 parts of the monoazo-dyestufi 4-hydroxy-l:l-azobenzene-3'-carboxylic acid. The susof the formula pension of the primary condensation product is neutralized with dilute sodium carbonate solution, and there is 20 COOH HO S0311 added to the suspension a neutral solution of 48 parts of i the amino-azo-dyestuffi of the formula HiN N=N NH Hots i and the whole is stirred for several hours at 35 C. It

is then heated with 20 parts of aniline for 3 hours at 90 7 p C. The diazo dyestuif is filtered off and converted into the mixture is stirred for 6 hours at 40 C., and the 6 its complex copper compound according to one of the reaction mixture is neutralized with sodium carbonate soth d d ib d, Th ew dyestufi dyes tt d lution of 10 per cent strength. The dyestuff is then isobrown ti t lated and dried. It dyes cotton by the single bath'or 2-bath after-coppering process yellow-brown tints of very good fastness to light and Washing. 100 parts of cotton are entered at 40 C. into a dye- When the third chlorine atom in the above dyestuff is bath, which contains in 3000 parts of water 1 part of reacted with aniline there is obtained a .dyestuff having the cupriferous dyestufi obtainable as described in the similar properties and corresponding to the formula first and second paragraphs of Example 1. Dyeing is COOH HO N l l Example 9 COOH \C% H038- 0 By using in this example, instead of 4 -amino-4-hycarried on for one hour while increasing the temperature droxy-l:1-azobenzene-3-carboxylic acid, the correspondto 90 C., 30 parts of crystalline sodium sulfate are ing quantity of 2-chloro-4-amino-4'-hydroxy-1:l-azobenadded, and dyeing is continued for a further /2 hour at zene-3-carboxylic acid, there is obtained a dyestufi which 90-95 C. The cotton is then rinsed and finished in the likewise dyes cotton yellow brown tints. usual manner. It is dyed brown, and the dyeing is distinguished by a very good fastness to light.

What is claimed is: 1. An azo-dysetuff of the formula Example 7 HOaS in which R1, R2 and Y each represent a benzene radical R1 containing in para-position with respect to the azo linkage a hydroxyl group and in ortho-position to the until the free amino group can no longer be detected.

The mineral acid formed in the reaction is continuously '65 neutralized by the addition of sodium carbonate. When latter group a carboxylic acid group, the azo-linkage and the treatment with phosgene has finished, the resulting the -NI-ICONH- group being bound to R2 in paraasymrnetrical urea derivative is filtered off and dried. position to each other, and Y containing a water solu- The dyestuif dissolves in water with a brown coloration bilizing group.

and dyes cotton brown tints when after-coppered. 2. The azo-dyestufi of the formula HO N=N OOH 3. The azo-dyestuif of the formula GOO--Cu-0 c0011 References Cited in the file of this patent UNITED STATES PATENTS 1,933,585 Bzightman et a1 Nov. 7, 1933 2,212,590 Delfs et a1 Aug. 27, 1940 2,228,321 Messmer et a1 Ian. 14, 1941 2,396,659 Kaiser Mar. 19, 1946 2,667,477 Liechfi 12111.26, 1954 

1. AN AZO-DYESTUFF OF THE FORMULA 